Introduction to In-Situ Chemical Oxidation Oxidation

Introduction to In-Situ Chemical
Oxidation
Douglas Larson, Ph.D., P.E.
Geosyntec Consultants
March 15-16, 2011
Introduction
•
•
•
•
•
Oxidation Chemistry
Oxidant Selection
Applicable Contaminants and Site Conditions
Remediation Timeframes
Safety Considerations
Slide 2
Technology Basis
• Addition of an oxidant to promote direct oxidative
destruction of organic contaminants to acceptable
end products (e.g., CO2, H2O, chloride)
• Various oxidants are in common use:
Catalyzed hydrogen peroxide
Ozone
Permanganates
Persulfate
Solid phase peroxygens
Potassium Permanganate
Delivery System
Technology Basis
• Oxidation is accomplished by the direct contact of a
reactive chemical species with the contaminant(s) of
concern
• Example: Hydrogen peroxide mixed with ferrous iron at
low pH results in formation of a hydroxyl radical which
acts as the reactive species:
1. Fe+2 + H2O2 → Fe+3 + OH· + OH2. Fe+3 + H2O2 → Fe+2 + OOH· + H+
Hydroxyl
Radical
• The radical then reacts with the contaminant, resulting in
non-regulated by-products and CO2
• Direct oxidation also occurs
Ozone, permanganate, peroxide and persulfate anion
Hydroxyl Radical
ISCO History
• Permanganate discovered to be a strong oxidizer in
1659; used for water treatment since early 1900s
• Fenton’s chemistry discovered in late 1800s
• Environmental applications of Fenton’s reagent
began in early to mid 1990s
• Permanganate for chlorinated ethenes began in
1989; well-established by late 1990s
• Ozone sparging for semi-volatiles began in late 1980s;
continued development to date
Johann Rudolf Glauber –
Discovered KMnO4 in 1659
• Interest in persulfate in mid to late 1990s;
commercial applications began in early 2000s
• In situ trials with other oxidants since the early 1990s;
catalyzed hydrogen peroxide (CHP), permanganate, and
persulfate are most widely used for in situ applications.
Slide 5
Evolution of Oxidant Use
• Hydrogen peroxide - 1980s
Fenton’s chemistry was violent, vigorous at best
21st Century – Catalyzed hydrogen peroxide (CHP)
• Ozone - early 1990s
• Permanganate - late 1990s
• Persulfate - 2002+
1000
mg/L
100
mg/L
10
mg/L
5 mg/L
1 mg/L
0 mg/L
• Solid Phase Peroxygens - 2004+
• Delivery Enhancements - 2007+
Surfactant-enhanced ISCO
Slide 6
Conceptual Design
Recirculation
In Situ Mixing
Direct Injection
ISCO - Pros and Cons
Pros
• Rapid treatment with mass
destruction, in-situ
• Selection of proper oxidant
allows of treatment of wide
spectrum of chemicals
• Applicable in overburden
and bedrock
• Appropriate for source
zones or “hot spots”
• Generally innocuous end
products
• Accepted by most
regulatory agencies
Cons
• Natural oxidant demand
(NOD) consumes oxidant
• Delivery limited by
heterogeneity or low
permeability
• Post-treatment rebound
• Can mobilize certain metals
• Health and safety concerns
• Often not cost effective for
dispersed or dilute plumes
• Injection and storage permit
requirements
Slide 8
Oxidant Selection
Oxidant
Oxidation
Potential (V)
Target Compounds
Permanganate
1.77
Chloroethenes, cresols,
chlorophenols, some
nitro-aromatics
Catalyzed Hydrogen Peroxide
(i.e., Fenton-like)
2.7
TPH, most organic
contaminants (inc. PCBs)
Ozone (O3 gas)
2.07
Chlorinated solvents,
phenols, MTBE, PAHs,
fuels and most organics
Persulfate
2.1
Activated Persulfate
2.6
BTEX, MTBE, 1,4dioxane, chlorinated
solvents, phenols, TCP,
PCBs, etc.
Slide 9
Trends in ISCO Field Deployment
Slide 10
Permanganate - NaMnO4 and KMnO4
MnO4- + 2H2O + 3e- → MnO2(s) + 4OH• Treats specific COCs (PCE, TCE, DCE, VC, some others)
• Direct oxidation at ambient pH
Lower power oxidant, cleaves double bonds
• Reaction rates – minutes to days
Can persist for weeks to months, reduces rebound
• Residual manganese dioxide – MnO2
Formation of rinds that can encapsulate solvents, can limit
treatment
Manganese Dioxide
Slide 11
Permanganate Reactions
Solubility (g/L)
−
4
KMnO4 → MnO + K
−
4
+
Potassium
Permanganate
Crystals
42
+
NaMnO4 → MnO + Na
900
Sodium
Permanganate
PCE Oxidation: 3C2Cl4 + 4MnO 4 + 4H2O
6CO2 + 12Cl- + 4MnO2(s) +
8H+
TCE Oxidation:
C2Cl3H + 2MnO-4
2CO2 + 3Cl- + 2MnO2(s) + H+
Slide 12
Permanganate Application
Permanganate in
Groundwater
Slide 13
Permanganate Application
Solid-Phase
Permanganate Delivery
Slide 14
Permanganate – Target Compounds
Slide 15
Permanganate – A Selective Oxidant
Works well for
Does not work well for
• Chlorinated ethenes
• Chlorinated ethanes or
• Probably chlorophenols &
cresols
methanes
• Most hydrocarbons (incl.
• Possibly alkynes,
alcohols, explosives,
sulfides, and others?
BTEX, fuels, creosote)
• Most pesticides
• PCBs
• Dioxins
• Oxygenates (MTBE, 1,4-
Dioxane)
TNT
TCE
Slide 16
Catalyzed Hydrogen Peroxide
H2O2 + Fe2+ OH• + OH- + Fe3+
(pH <3 to maintain iron solubility)
• OH • is highly reactive;
fast reactions, short half-life, exothermic
• H2O2 ends up as oxygen off-gas
• Modified Fenton’s recipes work at neutral pH
• Inject 5 to 25% peroxide (depending on vendor)
• Strongest oxidizer typically used for enviro. applications
Catalyzed Hydrogen Peroxide
• Much more complex chemistry than permanganate
Primary reactive species is hydroxyl radical (OH•)
Other transient oxygen species including superoxide anion (O2•-)
and hydroperoxide (HO2-), both of which are reductants
• CHP is transport limited
Highly reactive hydroxyl radicals can react with H2O2, carbonate,
& any transition metals (mineral forms of Fe & Mn)
Unlikely to persist longer than a few days in groundwater
• Strong oxidation can treat most organics
Heating and off-gas formation can be leveraged for treatment
Slide 18
Ozone - O3
O3 + HO2– → OH• + O2• – + O2
• Non-specific COC treatment (chlorinated solvents, PAHs, fuels
and most organics)
• Fast reaction rate – seconds to minutes
Transport limited – affects well spacing and injection rate
• Pulsed injection better than continuous sparging
Enhances aerobic microbial processes and desorption
• Can be effective for vadose zone treatment (but need moisture)
• Typically successful with lowest g/kg dosage
Ozone
Molecule
Slide 19
Ozone Sparging System
Slide 20
Persulfate - Na2S2O8
Men+ + S2O8 2 – → SO4 – • + Me(n +1)+ + SO42–
SO4 – • + RH → R • + HSO4–
• Can treat a wide range of COCs (solvents, etc.)
Can produce a broad range of oxidizing and reducing species
• Direct decomposition rate is slow
Promise of a low SOD oxidant
• Requires activation by:
Ferric iron/EDTA - Lower power and slower rate
Heat - Activation rate proportional to temperature
Base/Alkaline - Activation rate increases with pH
• By-products are sulfate and salts
• Used by consultants & vendors - proprietary processes
Surfactant-Enhanced ISCO
• Typically coupled with base-activated persulfate
• Designed to overcome dissolution rate limitations oxidation occurs across the liquid-solid/NAPL interface
• Improve sweep efficiency via viscosity reduction
• Achilles Heel
NAPL mobilization - both surfactant and elevated pH
reduce interfacial tensions
Surfactants exert an oxidant demand and increase
cost
• Applied by consultants, in tandem
with vendors / academics
Solid Phase Peroxygens
• Calcium peroxide - CaO2
BiOx®, Cool-Ox™, RegenOx™
• Calcium peroxide and sodium persulfate
Klozur® CR
• Designed to improve ease of handling and have
slow release characteristics
• Typically injected on a closely spaced grid
Transport limitations inherent
• In situ performance has been variable
Soil mixing can be cost competitive (depends on site
conditions
Slide 23
Integration with Other Technologies
Bioremediation (following ISCO)
Short-term: oxidants disinfect microbial communities in the
treatment zone & inhibit biodegradation
Long-term: oxidant products (MnO2, O2, or SO4) create
electron donor demand that must be overcome prior to
dechlorination
Groundwater/Vapor Extraction/MPE (with CHP)
Generation of heat/vapor may be used to mobilize VOC mass
Cosolvent/Surfactants (concurrent with ISCO)
To enhance dissolution from DNAPL during ISCO
Delivery is still the limiting factor
Thermal (before ISCO)
Residual heat used to activate persulfate
for post-thermal polishing
In Situ Thermal
Treatment
Design & Implementation
1. Oxidant Selection
Each class of oxidants has unique characteristics
– Contaminants that can be treated
– Reaction rates & activation chemistry
– Ability to distribute, persistence
– Impurities or by-products
Bench testing develops a site-specific basis for
oxidant/activator consumption rates and demands
Bench testing can assess treatability
of complex mixtures
Samples for
Bench Testing
Design & Implementation
2. Oxidant Demand
In addition to the target contaminants, various
factors place demand on (use up) the oxidant
• Natural oxidant demand (NOD)
• GW oxidant demand (GWOD)
Each contribute to required oxidant volume & cost
Site-specific oxidant demand can be tested in the
laboratory
Oxidant Demand
Test Kit
Natural Oxidant Demand (NOD)
• The consumption of oxidant due to reactions with
the background soil
• Usually attributed to oxidation of organic carbon
and reduced mineral species (esp. divalent Fe
and Mn, sulfides)
• Units: grams of oxidant per kg of soil
• Excludes demand exerted by contaminants
Slide 27
Measuring NOD
1. Theoretical NOD
Similar to ThBOD for wastewater (calculated based on the
chemical composition of the soil)
2. Batch reactors (i.e., BOD bottles)
Current protocol: ASTM D7262-07
Protocols similar for permanganate and persulfate
3. Modified COD
Standard wastewater analysis method (novel method)
High temperature digestion with permanganate
Correlates closely with 12 month batch reactor studies
Slide 28
Soil Type vs. Oxidant Demand
500
NM-30
FL-23
NM-29
NJ-22
100
MA-24
FL-28
WA-21
50
NM-32
MA-19
FL-14
10
GA-12
FL-9
WA-20
CA-16
PA-18
SC-8
FL-10
NJ-15
FL-6
5
1.0
0.5
FL-27
FL-7
SC-34
FL-25
FL-26
TX-5
NC-17
AR-4
GA-3
MO-33
AZ-2
CA-1
0.1
Bed- Coarse
Rock Sand
Fine
Sand
Silty
Sand
Clayey
Sand
Sandy
Clay
Silty
Clay
Clay
Peat /
Humic
48-HR MATRIX OXIDANT DEMAND (g/kg)
Initial Oxidant Concentration Affects
Observed Oxidant Demand
35
30
25
20
15
10
5
0
0
2
4
6
8
10
12
14
INITIAL SODIUM PERMANGANATE CONCENTRATION (g/L)
16
Design & Implementation
3. Dosing/Injection Strategy
Most common delivery method is batch injection
using direct push techniques (DPT – Geoprobe)
Tendency toward low volume and high oxidant
concentration (to deliver oxidant dose quickly)
This approach often fails – longer (or repeat)
injections at lower concentration may be better
Organic
Carbon
Soil
Grain
Soil
Grain
Chem. Ox.
C1
C2 > C1
Design & Implementation
4. Achieving Oxidant Distribution
Direct injection can result in uneven distribution
Recirculation (even temporary) can improve
distribution
Creative combinations work – pulsing, semi-
constant head, recirculation, pull-push
High-energy methods – larger diameter auger
and fracturing
Slide 32
Heterogeneity
Slide 33
Impacts of Stratigraphy
Slide 34
Gas-Phase Delivery (Ozone)
Ozone
Generator
Hydraulic Conductivity
Both Scenarios: Extract and Reinject @ 20 gpm for 15 hours
Contour interval on both maps = 0.2 ft.
6.80
6.74
Extract (20 gpm) - Inject (20 gpm) 15 hours (18000 gallons) K=100 ft/d
6.8
6
Extract (20 gpm) - Inject (20 gpm) 15 hours (18000 gallons) K=300 ft/d
6.
54
6.68
6.58
HA-13
46
6.
78
6.
6.
62
6.
6.7
0
MW-07
330
7.02
7.06
HA-14
86
66..82
1900
2
6.94
6.7
74
6.
MW-08
6.84
6.80
6.90
HA-6
HA-11
HA-12
1600
6.98
HA-12
1600
76
6.
7.
10
6.
94
HA-14
27
6.90
66
HA-9
330
6.88
6.50
6.42
27
PEEDWAY AVENUE
6.84
2
6.7
6.58
HA-13
MW-07
HA-6
HA-11
MW-08
1900
6.7
0
4000
4000
21 feet
21 feet
HA-5
HA-5
MW-10
6.78
MW09
120
MW-10
HA-4
4000
HA-10
K = 100 ft/d
6.9
MW09
0
120
HA-7
6.84
HA-4
4000
HA-10
K = 300 ft/d
Slide 38
Factors Affecting Remediation Time
•
•
•
•
Oxidant selection
Oxidant dose
Contaminant distribution
Soil organic carbon content and oxidant
demand
• Site hydrogeology
• Remedial Action Objectives
• Stakeholder considerations
Slide 39
Safety Considerations
• Mixing with incompatible materials may cause
explosive decomposition
• Spills onto combustible materials can cause fires
• Health hazards are acute, not chronic
• Peroxide decomposes into water and oxygen
which can promote flammable conditions
Reaction of
permanganate with
glycerol
Skin immediately after
30% H2O2 exposure
Slide 40
Safety Considerations
Some EH&S scenarios to plan for:
• Surfacing of amendment
• Identification of preferential pathways
• Splash and pressurized line hazards
• Decontamination and container
management
Permanganate
Surfacing in a Bay
Slide 41
Permitting
• National Fire Protection Association (NFPA
430)
Storage and handling of liquid or solid oxidizers -
notify authority having jurisdiction
Emergency Response training program required
0
Signage required
0
1
OX
• Underground Injection Control (UIC) permitting
• Other state requirements (e.g., Remedial
Additive Requirements per MCP in MA)
Slide 42
Homeland Security Requirements
• Chemical Facilities Anti-Terrorism
Standards (CFATS)
• H2O2 and KMnO4 are listed chemicals of
interest if:
H2O2 ≥ 35% concentration
Either > 400 lbs
• Storage facility required to submit a
Chemical Security Assessment Tool
(CSAT) Top-Screen.
• Permanganates also regulated by DEA
Slide 43
Questions?
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•
•
•
•
Oxidation Chemistry
Oxidant Selection
Applicable Contaminants and Site Conditions
Remediation Timeframes
Safety Considerations
Slide 44
Contact Information
Douglas Larson, Ph.D., P.E.
Geosyntec Consultants, Inc.
289 Great Road, Suite 105
Acton, Massachusetts 01720
(978) 206-5774
dlarson@geosyntec.com
Slide 45